Adhesive film

ABSTRACT

An adhesive film used for bonding a semiconductor component or a liquid crystal display component with a substrate, the adhesive film being composed of a resin composition containing a curable resin and a filler, and the adhesive film showing a water vapor transmission rate of 30 [g/m 2 ·24 h] or above, wherein the curable resin preferably contains photo-curable resin, thermosetting resin, or curable resin cured both by light and heat. The filler preferably contains a porous filler, the filler preferably has a mean void diameter of 0.1 to 5 nm, and the adhesive film preferably shows a water vapor transmission rate at 25° C. of 4 [g/m 2 ·24 h] or above.

TECHNICAL FIELD

The present invention relates to an adhesive film.

BACKGROUND ART

In the process of bonding a semiconductor component such assemiconductor element or a liquid crystal display component, with asubstrate such as rigid substrate represented by interposer, or aninsulating substrate composed of organic or inorganic material, a liquidresin, for example, which serves as an adhesive is typically used asbeing selectively coated on either one of the semiconductor element andthe substrate by using a dispenser or by potting, or as being partiallycoated typically using a squeegee (see Patent Document 1, for example).

Depending on types of the semiconductor component or liquid crystaldisplay component, in the process of bonding the component and thesubstrate, the adhesive is selectively coated only to the peripheralportion, and the component and the substrate are bonded so as to obtaina structure having a space formed therein (so-called hollow package),rather than bonding them by coating the adhesive over the entiresurface. In particular, if a general adhesive is applied to suchstructure using a transparent component such as glass as the substrate,the transparent component may get dewed in the inner space. Inparticular for the case where the semiconductor component is asolid-state image sensor, the dewing may prevent the solid-state imagesensor from exactly taking part in photo-electric conversion, and mayraise problems in image recognition and display.

[Patent Document 1] Japanese Laid-Open Patent Publication No.H10-313070.

DISCLOSURE OF THE INVENTION

An object of the present invention is to provide a highly reliableadhesive film capable of preventing dewing possibly occurs between thesemiconductor component or liquid crystal display component, and thesubstrate.

The object may be achieved by the present invention described in (1) to(16) below.

(1) An adhesive film used for bonding a semiconductor component or aliquid crystal display component with a substrate,

wherein the adhesive film is composed of a resin composition containinga curable resin and a filler, and the adhesive film shows a water vaportransmission rate, measured conforming to JIS Z0208 Method-B, of 30[g/m²·24 h] or above.

(2) The adhesive film as described in (1), wherein the curable resincontains a photo-curable resin.

(3) The adhesive film as described in (2), wherein the photo-curableresin contains a ultraviolet curable resin having an acrylic compound asa major constituent.

(4) The adhesive film as described in (1), wherein the curable resincontains a thermosetting resin.

(5) The adhesive film as described in (4), wherein the thermosettingresin contains an epoxy resin.

(6) The adhesive film as described in (1), wherein the curable resincontains a curable resin curable both by light and heat.

(7) The adhesive film as described in (6), wherein the curable resincurable both by light and heat contains a (meth)acryl-modified phenolresin or (meth)acryloyl-group-containing (meth)acrylic acid polymer.

(8) The adhesive film as described in (1), wherein the filler contains aporous filler.

(9) The adhesive film as described in (8), wherein the filler has a meanvoid diameter of 0.1 to 5 nm.

(10) The adhesive film as described in (8), wherein the filler shows anadsorptivity [Q1] under room temperature (increase in weight of thefiller completely dried under heating and weighed in an aluminum cup,after allowed to stand in a 25° C./50% environment for 168 hours) of 7[g/100 g filler] or above.

(11) The adhesive film as described in (10), wherein the filler shows anadsorptivity [Q2] at 60° C. (increase in weight of the filler completelydried under heating and weighed in an aluminum cup, after allowed tostand in a 60° C./90% environment for 168 hours) of 3 [g/100 g filler]or above.

(12) The adhesive film as described in (11), satisfying 0.4×[Q1]<[Q2]

(13) The adhesive film as described in (8), wherein the filler iszeolite.

(14) The adhesive film as described in (1), wherein the adhesive filmshows a water vapor transmission rate, measured conforming to JIS Z0208Method-B, of 200 [g/m²·24 h] or below.

(15) The adhesive film as described in (1), wherein the adhesive filmshows a water vapor transmission rate at 25° C. (measured conforming toJIS Z0208, under conditions of moisture permeation treatment of 25°C./50%) of 4 [g/m²·24 h] or above.

(16) The adhesive film as described in (1), wherein the substrate showsa water vapor transmission rate, measured conforming to JIS Z0208Method-B, of less than 30 [g/m²·24 h].

According to the present invention, there is provided a highly reliableadhesive film capable of preventing dewing possibly occurs between asemiconductor component or a liquid crystal display component, and asubstrate. The adhesive film scarcely causes corrosion of internalelectrodes, and may keep the reliability for long period.

BEST MODES FOR CARRYING OUT THE INVENTION

The adhesive film of the present invention will be detailed below. Theadhesive film of the present invention is the one used for bonding asemiconductor component or a liquid crystal display component with asubstrate, wherein the adhesive film is composed of a resin compositioncontaining a curable resin and a filler, and shows a water vaportransmission rate of 30 [g/m²·24 h] or above.

The adhesive film of the present invention is used for bonding asemiconductor component or a liquid crystal display component with asubstrate. In the bonding of a semiconductor component or a liquidcrystal display component with a substrate, it is necessary that anadhesive component is formed precisely to a predetermined portion of thesemiconductor component or the like (or substrate). The adhesive film ofthe present invention is suitable for the requirement.

The adhesive film is composed of a resin composition containing acurable resin and a filler, wherein the adhesive film shows a watervapor transmission rate of 30 [g/m²·24 h] or above. By virtue of thisconfiguration, even when the film is used for adhesion of asemiconductor component or a liquid crystal display component with asubstrate, the substrate (in particular, transparent substrate) or thelike may be prevented from getting dewed due to internal moisture.

In order to prevent the substrate or the like from getting dewed due tomoisture, there has been known to control water vapor transmission rateof the adhesive and so forth. A method of lowering the water vaportransmission rate of the adhesive and so forth (to as low as 10 [g/m²·24h] or below, for example) in order to prevent the dewing has beenexamined, only to find difficulty.

In contrast, the present invention prevents occurrence of the dewing,not by lowering the water vapor transmission rate of the adhesive filmas being conventionally practiced, but conversely by raising it so as tomake the film improved in the gas permeability.

Water vapor transmission rate of the adhesive film is preferably[g/m²·24 h] or above, and more preferably 50 to 200 [g/m²·24 h]. Thewater vapor transmission rate lower than the lower limit value mayresult in insufficient prevention of dewing of the substrate and soforth. The water vapor transmission rate exceeding the upper limit maydegrade film-forming performance.

The water vapor transmission rate of the adhesive film may be evaluatedby using a 100-μm-thick adhesive film, conforming to the moisturepermeable cup method (JIS Z0208 Method-B), at 40° C./90%.

Water vapor transmission rate of the adhesive film at 25° C. ispreferably adjusted to 4 [g/m²·24 h] or above. In this way, inparticular the substrate or the like may effectively be prevented fromgetting dewed. The water vapor transmission rate of the adhesive film at25° C. may be evaluated using an adhesive film of 100 μm thick,conforming to the water vapor permeability cup method (JIS Z0208), underconditions for water vapor permeation treatment of 25° C./50%.

Reason why the adhesive film of the present invention can prevent dewingmay be supposed as follows.

For example, dewing occurred between the semiconductor component and thesubstrate (inner space) may be supposedly ascribable to moistureconfined into the inner space in the process of bonding, and moisturecoming into the inner space through the adhesive layer after thebonding. A method of lowering water vapor transmission rate of theadhesive film could not completely reduce the water vapor transmissionrate to zero, instead allowing moisture to slowly enter the inner spaceover a long period of time, while being incapable of releasing it to theexternal, making it difficult to solve the problem of dewing. Incontrast, the adhesive film of the present invention has a relativelylarge water vapor transmission rate, capable of immediately releasingmoisture occurred in the inner space to the extend, and thereby thedewing may effectively be prevented.

The curable resin composing the resin composition may be exemplified byphoto-curable resin (resin curable mainly by irradiation of light suchas ultraviolet radiation), and thermosetting resin (resin curable mainlyby heat).

The curable resin preferably contains the photo-curable resin, althoughnot specifically limited. In this way, accuracy of alignment of theadhesive component may be improved. This is because inclusion of thephoto-curable resin may facilitate placement of the adhesive film to apredetermined position, through light exposure, development, andpatterning.

The photo-curable resin (in particular, ultraviolet curable resin) maybe exemplified by ultraviolet curable resins having acrylic compound asa major constituent; ultraviolet curable resin having urethane acrylateoligomer or polyester urethane acrylate oligomer as a major constituent;and ultraviolet curable resin having at least either one selected fromthe group consisting of epoxy-base resin and vinyl-phenol-base resin.

Among these, the ultraviolet curable resin having acrylic compound as amajor constituent is preferable. The acrylic compound shows rapid rateof curing when irradiated with light, so as to allow the resin to bepatterned only with a relatively small energy of light exposure. Theacrylic compound may be exemplified by monomers of acrylic acid estersor methacrylic acid esters, and more specifically by bifunctionalacrylates such as ethylene glycol diacrylate, ethylene glycoldimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanedioldimethacrylate, glycerin diacrylate, glycerin dimethacrylate,1,10-decanediol diacrylate, 1,10-decanediol dimethacrylate; andmultifunctional acrylates such as trimethylolpropane triacrylate,trimethylolpropane trimethacrylate, pentaerythritol triacrylate,pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, anddipentaerythritol hexamethacrylate. Among these, acrylic acid esters arepreferable, and acrylic acid esters or methacrylic alkyl esters having 1to 15 carbon atoms in the ester portions thereof are particularlypreferable.

Content of the photo-curable resin (ultraviolet curable resin) ispreferably 5 to 60 wt % of the whole resin composition, and morepreferably 8 to 30 wt %, although not specifically limited. The contentbelow the lower limit value may inhibit patterning of the resin byultraviolet irradiation, whereas the content exceeding the upper limitvalue may make the resin too soft, and may degrade film characteristicsbefore ultraviolet irradiation.

The photo-curable resin (in particular, ultraviolet curable resin)preferably exist in a liquid format normal temperature, although notspecifically limited. As a consequence, reactivity inultraviolet-induced curing may be improved. In addition, operation ofmixing it with the thermosetting resin may be facilitated. Theultraviolet curable resin exists in a liquid form at room temperaturemay be exemplified by ultraviolet curable resin having theabove-described acryl compounds as the major constituent.

The resin composition may more preferably be used as being combined witha photo-polymerization initiator. In this way, the resin may efficientlybe patterned based on photo-polymerization.

The photo-polymerization initiator may be exemplified by benzophenon,acetophenone, benzoin, benzoin isobutyl ether, methyl benzoyl benzoicacid, benzoyl benzoic acid, benzoin methyl ether, benzylphenyl sulfide,benzyl, dibenzyl, and diacetyl.

Content of the photo-polymerization initiator is preferably 0.5 to 5 wt% of the whole resin composition, and more preferably 0.8 to 2.5 wt %,although not specifically limited. The content smaller than the lowerlimit value may degrade the effect of initiating thephoto-polymerization, whereas the content exceeding the upper limitvalue may make the reactivity too large, and may thereby degrade thestorability and resolution performance.

It is preferable that the curable resin additionally contains athermosetting resin. In this way, the adhesive film may retainadhesiveness even after light exposure, development and patterning. Morespecifically, the semiconductor component or the like may be bonded tothe substrate, by disposing the adhesive component at a predeterminedposition by placing the adhesive film and by subjecting it to lightexposure, development and patterning, followed by thermocompressionbonding.

The thermosetting resin may be exemplified by novolac-type phenol resinssuch as phenol novolac resin, cresol novolac resin and bisphenol-Anovolac resin; phenol resins such as resol phenol resin; bisphenol-typeepoxy resins such as bisphenol-A epoxy resin and bisphenol-F epoxyresin; novolac-type epoxy resins such as novolac epoxy resin and cresolnovolac epoxy resin; epoxy resins such as biphenyl-type epoxy resin,stilbene-type epoxy resin, triphenol methane-type epoxy resin,alkyl-modified triphenol methane-type epoxy resin, triazinekernel-containing epoxy resin, and dicyclopentadiene-modifiedphenol-type epoxy resin; triazine-ring-containing resins such as urearesin and melamine resin; unsaturated polyester resin; bismaleimideresin; polyurethane resin; diallyl phthalate resin; silicone resin;benzooxazine-ring-containing resin; and cyanate ester resin, whereinthey may be used independently or in a mixed manner. Among these, epoxyresins are particularly preferable. In this way, the heat resistance andadhesiveness may further be improved.

It is further preferable to use, as the above-described epoxy resins, anepoxy resin which exists in a solid form at room temperature (inparticular, bisphenol-type epoxy resin), in combination with an epoxyresin which exists in a liquid form at room temperature (in particular,silicone-modified epoxy resin which exists in a liquid form at roomtemperature). In this way, the flexibility and resolution performancemay be improved while keeping the heat resistance.

Content of the thermosetting resin is preferably 10 to 40 wt % of thewhole resin composition, and more preferably 15 to 35 wt %, although notspecifically limited. The content smaller than the lower limit value maydegrade an effect of improving the heat resistance, whereas the contentexceeding the upper limit value may degrade an effect of improvingtoughness of the adhesive film.

For the case where the thermosetting resin which exists in a liquid format room temperature is used in combination, the total amount of theliquid photo-curable resin and the liquid thermosetting resin ispreferably 60% weight or below of the total weight of resin composition,and more preferably 50 wt % or below. The lower limit is preferably setto 5 wt % or above, although not specifically limited. The contentfallen in this range may ensure, in particular, heat resistance,flexibility and resolution performance well balanced thereamong.

The curable resin further preferably contains a curable resin curableboth by light and heat. In this way, compatibility between thephoto-curable resin and the thermosetting resin may be improved, therebystrength of the adhesive film after being cured (photo-cured andheat-cured) may be improved, and reliability of the final product mayconsequently be improved.

The curable resin curable both by light and heat may be exemplified bythermosetting resins having photo-functional groups such as acryloylgroup, methacryloyl group and vinyl group; and photo-curable resinshaving heat-reactive groups such as epoxy group, phenolic hydroxylgroup, alcoholic hydroxyl group, carboxyl group, acid anhydride group,amino group, and cyanate group. More specifically, (meth)acryl-modifiedphenol resin, and acryl copolymer resin having carboxyl groups and acrylgroups in the side chains thereof, may be exemplified. Among these,(meth)acryl-modified phenol resin is preferable. The selection allowsuse of alkaline aqueous solution, less causative of environmentalimpact, as a developing solution in place of organic solvent, whilekeeping the heat resistance. The curable resin adoptable herein may bethose described for the thermosetting resin and photo-curable resin.

As for the thermosetting resin having the photo-reactive group, ratio ofmodification (ratio of substitution) of the photo-reactive group ispreferably 20 to 80% of the total reactive group of curable resincurable both by light and heat (total content of photo-reactive groupand heat-reactive group), and more preferably 30 to 70%, although notspecifically limited. The ratio of modification in the above-describedrange may ensure especially excellent resolution performance.

As for the photo-curable resin having the heat-reactive group, ratio ofmodification (ratio of substitution) of the heat-reactive group ispreferably 20 to 80% of the total reactive group of curable resincurable both by light and heat (total content of photo-reactive groupand heat-reactive group), and more preferably 30 to 70%, although notspecifically limited. The ratio of modification in the above-describedrange may ensure especially excellent resolution performance.

Content of the curable resin curable both by light and heat ispreferably 15 to 50 wt % of the whole the resin composition, and morepreferably 20 to 40 wt %, although not specifically limited. The contentsmaller than the lower limit value may degrade an effect of improvingthe compatibility, whereas the content exceeding the upper limit valuemay degrade the developability and resolution performance.

The resin composition contains a filler. The filler is an importantcomponent for controlling water vapor transmission rate of the adhesivefilm. The filler may be exemplified by fibrous fillers such as aluminafiber and glass fiber; needle-like fillers such as potassium titanate,wollastonite, aluminum borate, needle-like magnesium hydroxide, andwhisker; plate-like fillers such as talc, mica, sericite, glass flake,scaly graphite, and plate-like calcium carbonate; spherical (granular)filler such as calcium carbonate, silica, fused silica, sintered clay,and unsintered clay; and porous fillers such as zeolite and silica gel.A single species of them may be used, or two or more species may be usedin a mixed manner. Among these, porous fillers are preferable. In thisway, the adhesive film may be increased in the water vapor transmissionrate.

Average particle size of the filler is preferably 0.01 to 90 μm, andmore preferably 0.1 to 40 μm, although not specifically limited. Theaverage particle size exceeding the upper limit value may induceabnormality in appearance of film and resolution failure, whereas themean particle size smaller than the lower limit value may result inbonding failure in the process of bonding under heating. The meanparticle size may be evaluated, typically by using a laser diffractionparticle size analyzer SALD-7000 (from Shimadzu Corporation).

Content of the filler is preferably 5 to 70 wt % of the whole resincomposition, and more preferably 20 to 50 wt %, although notspecifically limited. The content exceeding the upper limit value mayinduce bonding failure in the process of bonding under heating, whereasthe content smaller than the lower limit value may fail in improvingdewing of the substrate, because of insufficient water vaportransmission rate.

As the filler, a porous filler is preferably used. When a porous filleris used as the filler, the porous filler preferably has a mean voiddiameter of 0.1 to 5 nm, and more preferably 0.3 to 1 nm. If the meanvoid diameter exceeds the upper limit value, a part of resin componentmay enter the voids so as to inhibit the reaction, whereas if the meanvoid diameter is smaller than the lower limit value, the film maydegrade the water vapor transmission rate due to lowered moistureabsorption performance, and may fail in improving the dewing of thesubstrate. Molecular Sieve composed of a crystalline zeolite mayspecifically be exemplified as the porous filler. The crystallinezeolite is expressed by the formula below:M_(2/n)O.Al₂O₃.xSiO₂.yH₂O

M: metal cation, n: valency.

Crystal types of the crystalline zeolite may be exemplified by 3A, 4A,5A and 13X, wherein 3A-type and 4A-type are preferably used from theviewpoint of effectively preventing the dewing.

Adsorptivity [Q1] at room temperature of the filler is not specificallylimited, but is preferably 7 [g/100 g filler] or above, and morepreferably 15 [g/100 g filler] or above. The adsorptive force at roomtemperature smaller than the lower limit value may fail in improving thedewing of the substrate, because of insufficient water absorptionperformance of the filler, and of decrease in water vapor transmissionrate of the film. The adsorptivity [Q1] at room temperature may bedetermined based on increase in weight observed after weighing thefiller completely dried by heating in an aluminum cup, and allowing itto stand in a 25° C./50% environment for 168 hours.

Adsorptivity [Q2] at 60° C. of the filler is preferably 3 [g/100 gfiller] or above, and more preferably 10 [g/100 g filler] or above,although not specifically limited. The adsorptivity kept at theabove-described value even under 60° C. may be effective particularlyfor improving dewing of the substrate. The adsorptivity [Q2] at 60° C.may be determined based on increase in weight observed after weighingthe filler completely dried by heating in an aluminum cup, and allowingit to stand in a 60° C./90% environment for 168 hours.

The adsorptivity [Q1] at room temperature and the adsorptivity [Q2] at60° C. preferably satisfy the relation below, although not specificallylimited: 0.4*[Q1]<[Q2] When [Q1] and [Q2] satisfy the relation in theabove, a particularly large effect of improving dewing of the substratemay be obtained. This is supposedly because the filler retains theadsorptivity even under high temperatures, thereby the film filledtherewith retains water vapor transmission rate at relatively hightemperatures, allowing gaseous moisture to readily pass therethrough, sothat moisture in semiconductor devices or liquid crystal devices caninstantaneously be reduced even if the temperature is lowered from hightemperatures to room temperature, so as to avoid phenomenon of dewing.

The resin composition may contain, in addition to the above-describedcurable resin and filler, additives such as plastic resin, levelingagent, defoaming agent and coupling agent, so far as the objects of thepresent invention will not be impaired.

The semiconductor component bonded using the above-described adhesivefilm may be exemplified by solid-state image sensors such as CCD andCMOS, and semiconductor elements such as MEMS element, although notspecifically limited. The liquid crystal display component may beexemplified by liquid crystal panel, although not specifically limited.

The substrate may be exemplified by flexible substrates and rigidsubstrates such as those called as interposer or mother board; insulatedsubstrates composed of organic or inorganic material; and transparentsubstrates composed of acryl resin, polyethylene terephthalate resin(PET) and glass substrate. When the substrates, among these, composed ofinorganic material are used, performance of the adhesive film may fullybe expressed. This is supposedly because, if the substrates composed oforganic material should otherwise be used, the adhesive film may exertonly a small influence because the substrate is larger in the watervapor transmission rate as compared with the substrate composed ofinorganic material. In contrast, if the substrate composed of inorganicmaterial is used, only the portion of the adhesive film may be given asbeing water-transmissive, and may exert larger influence. Water vaportransmission rate of the substrate is preferably less than 30 [g/m²·24h].

EXAMPLES

The present invention will be explained in detail below, referring toExamples and Comparative Examples, without being limited thereto. First,Examples of the adhesive film will be explained. As for Molecular Sieveused in Examples, expression of “Molecular Sieve 3A” indicates that thecrystal type thereof belongs to 3A type.

Example 1

1. Curable Resin Curable Both by Light and Heat (Synthesis ofAcryl-Modified Phenol Resin)

Six hundred grams (OH equivalence of approximately 4) of a 70% MEKsolution of non-volatile fraction of phenol novolac (PhenoliteTD-2090-60M, from DIC Corporation) was placed in a 2-L flask, 1 g oftributylamine, and 0.2 g of hydroquinone were added thereto, and themixture was heated to 110° C. Further therein, 284 g (2 mol) glycidylmethacrylate was added dropwise over 30 minutes, the mixture was allowedto react at 110° C. for 5 hours under stirring, to thereby obtainmethacryloyl-group-containing phenol novolac (rate of modification withmethacryloyl group: 50%) having a non-volatile content of 80%.

2. Preparation of Resin Varnish

A resin varnish was prepared by weighing 5.1 wt % of acryl resincompound (triethylene glycol dimethacrylate; Neomer PM201 from SanyoChemical Industries, Ltd.) which exists in a liquid form at roomtemperature as the photo-curable resin, 12.9 wt % of epoxy resin(Epiclon N-865 from DIC Corporation) and 5.4 wt % of silicone epoxyresin (BY16-115 from Dow Corning Toray Co., Ltd.) as the thermosettingresins, 28.2 wt % of (meth)acryl-modified phenol resin synthesized inthe above as the curable resin curable both by light and heat, 1.9 wt %of photo-polymerization initiator (Irgacure 651 from Ciba SpecialtyChemicals Inc.), 31.8 wt % of porous filler (Molecular Sieve 3A fromUnion Showa K.K.) as the filler, and 14.7 wt % of methyl ethyl ketone asthe solvent, and the mixture was stirred using a disperser at a numberof rotation of 5,000 rpm for 1 hour.

3. Manufacture of Adhesive Film

The above-described resin varnish was coated by using a comma coateronto a polyester film (T100G from Mitsubishi Polyester Film Corporation,25 μm thick) as a support base, and dried at 80° C. for 10 minutes tothereby obtain an adhesive film of 50 μm thick.

Example 2

All procedures were similar to those described in Example 1, except thatthe resin varnish was mixed as described below. Mixed were 4.4 wt % ofacryl resin compound (Neomer PM201 from Sanyo Chemical Industries, Ltd.)which exist in a liquid form at room temperature as the photo-curableresin, 11.1 wt % of epoxy resin (Epiclon N-865 from DIC Corporation) and4.7 wt % of silicone epoxy resin (BY16-115 from Dow Corning Toray Co.,Ltd.) as the thermosetting resins, 24.3 wt % of (meth)acryl-modifiedphenol resin synthesized in the above as the curable resin curable bothby light and heat, 1.6 wt % of photo-polymerization initiator (Irgacure651 from Ciba Specialty Chemicals Inc.), 41.2 wt % of porous filler(Molecular Sieve 3A from Union Showa K.K.) as the filler, and 12.7 wt %of methyl ethyl ketone as the solvent.

Example 3

All procedures were similar to those described in Example 1, except thatthe resin varnish was mixed as described below. Mixed were 5.5 wt % ofacryl resin compound (Neomer PM201 from Sanyo Chemical Industries, Ltd.)which exists in a liquid form at room temperature as the photo-curableresin, 14.1 wt % of epoxy resin (Epiclon N-865 from DIC Corporation) and5.9 wt % of silicone epoxy resin (BY16-115 from Dow Corning Toray Co.,Ltd.) as the thermosetting resins, 30.7 wt % of (meth)acryl-modifiedphenol resin synthesized in the above as the curable resin curable bothby light and heat, 2.1 wt % of photo-polymerization initiator (Irgacure651 from Ciba Specialty Chemicals Inc.), 25.7 wt % of porous filler(Molecular Sieve 3A from Union Showa K.K., void diameter 3 Å) as thefiller, and 16.0 wt % of methyl ethyl ketone as the solvent.

Example 4

All procedures were similar to those described in Example 1, except thata filler described below was used. A porous filler (Molecular Sieve 4Afrom Union Showa K.K., void size=4 Å) was used as the filler.

Example 5

All procedures were similar to those described in Example 1, except thata filler described below was used. A porous filler (Molecular Sieve 13Xfrom Union Showa K.K., void size=5 Å) was used as the filler.

Example 6

All procedures were similar to those described in Example 1, except thata filler described below was used. A porous filler (Molecular Sieve 13Xfrom Union Showa K.K., void size=10 Å) was used as the filler.

Example 7

All procedures were similar to those described in Example 1, except thata resin curable both by light and heat described below was used. Anacryl copolymer resin (Cyclomer P from Daicel Chemical Industries,Ltd.), having carboxyl groups and acryl groups thereof, was used as theresin curable both by light and heat.

Example 8

All procedures were similar to those described in Example 1, except thatthe resin varnish was mixed as described below. Mixed were 5.1 wt % ofacryl resin compound (Neomer PM201 from Sanyo Chemical Industries, Ltd.)which exists in a liquid form at room temperature as the photo-curableresin, 12.9 wt % of epoxy resin (Epiclon N-865 from DIC Corporation) and5.4 wt % of silicone epoxy resin (BY16-115 from Dow Corning Toray Co.,Ltd.) as the thermosetting resins, 28.2 wt % of (meth)acryl-modifiedphenol resin synthesized in the above as the curable resin curable bothby light and heat, 1.9 wt % of photo-polymerization initiator (Irgacure651 from Ciba Specialty Chemicals Inc.), 15.9 wt % of porous filler(from Union Showa K.K., Molecular Sieve 3A) as the filler, 15.9 wt % ofsilica (Admafine SE5101 from Admatechs Co., Ltd.), and 14.7 wt % ofmethyl ethyl ketone as the solvent.

Example 9

All procedures were similar to those described in Example 1, except thatthe resin varnish was mixed as described below. Mixed were 5.1 wt % ofacryl resin compound (Neomer PM201 from Sanyo Chemical Industries, Ltd.)which exists in a liquid form at room temperature as the photo-curableresin, 12.9 wt % of epoxy resin (Epiclon N-865 from DIC Corporation) and5.4 wt % of silicone epoxy resin (BY16-115 from Dow Corning Toray Co.,Ltd.) as the thermosetting resins, 28.2 wt % of (meth)acryl-modifiedphenol resin synthesized in the above as the curable resin curable bothby light and heat, 1.9 wt % of photo-polymerization initiator (Irgacure651 from Ciba Specialty Chemicals Inc.), 15.9 wt % of porous filler(Molecular Sieve 3A from Union Showa K.K.) as the filler, 15.9 wt % ofsilica gel (Mizusawa Industrial Chemicals, Ltd.), and 14.7 wt % ofmethyl ethyl ketone as the solvent.

Comparative Example 1

All procedures were similar to those described in Example 1, except thatthe resin varnish was mixed as described below. Mixed were 5.1 wt % ofacryl resin compound (Neomer PM201 from Sanyo Chemical Industries, Ltd.)which exists in a liquid form at room temperature as the photo-curableresin, 12.9 wt % of epoxy resin (Epiclon N-865 from DIC Corporation) and5.4 wt % of silicone epoxy resin (BY16-115 from Dow Corning Toray Co.,Ltd.) as the thermosetting resins, 28.2 wt % of (meth)acryl-modifiedphenol resin synthesized in the above as the curable resin curable bothby light and heat, 1.9 wt % of photo-polymerization initiator (Irgacure651 from Ciba Specialty Chemicals Inc.), 31.8 wt % of silica (AdmafineSE5101 from Admatechs Co., Ltd.) as the filler, and 14.7 wt % of methylethyl ketone as the solvent.

Comparative Example 2

All procedures were similar to those described in Example 1, except thatthe resin varnish was mixed as described below. Mixed were 8.1 wt % ofacryl resin compound (Neomer PM201 from Sanyo Chemical Industries, Ltd.)which exists in a liquid form at room temperature as the photo-curableresin, 20.5 wt % of epoxy resin (Epiclon N-865 from DIC Corporation) and8.6 wt % silicone epoxy resin (BY16-115 from Dow Corning Toray Co.,Ltd.) as the thermosetting resins, 44.8 wt % of (meth)acryl-modifiedphenol resin synthesized in the above as the curable resin curable bothby light and heat, 3.0 wt % of photo-polymerization initiator (Irgacure651 from Ciba Specialty Chemicals Inc.), and 15.0 wt % of methyl ethylketone as the solvent.

The adhesive films obtained by the individual Examples and ComparativeExamples were evaluated as follows. Items to be evaluated are showntogether with the details. Obtained results are shown in Table 1.

1) Film Characteristics (Tensile Fracture Strength)

The obtained adhesive films were exposed to light of 365 nm so as toirradiate light to as much as 750 mJ/cm², and allowed to cure at 120° C.for 1 hour, and to further cure at 180° C. for 2 hours, to therebyobtain a cured film. Dumbbell specimens were manufactured from the curedfilm conforming to JIS K7127, and subjected to tensile test. Tensilefracture strength of the individual adhesive films was measured.

2) Developability

The obtained adhesive films were immersed in 3% TMAH(tetramethylammonium hydroxide) at 25° C., and developability was judgedas “yes” if the resin dissolved within 3 minutes rather than remainingon the polyester film as a support base, and judged as “no” if the resinremained.

3) Resolution Performance (Numerical Aperture)

Resolution performance was evaluated based on numerical aperture asdescribed below. Each of the obtained adhesive films was laminated to apolyimide film at 55° C., and subjected to pattern-forming exposureusing a negative film mask for forming a 200=μm-diameter via, allowingtherethrough light of 365 nm to be irradiated to as much as 200 mJ/cm².Thereafter, the film was developed using 3% TMAH at a pressure ofspraying of 0.1 MPa for 90 seconds, diameter of the patterned via wasmeasured under a measuring microscope, and the numerical aperture wascalculated using the equation below.Numerical aperture (%)=Diameter of opening actually measured(μm)/diameter of mask 200(μm)×1004) Water Vapor Transmission Rate

Using a laminator set to 60° C., the obtained adhesive films were bondedto manufacture a film of 100 μm thick, exposed by light using anexposure apparatus at an energy of exposure of 750 mJ/cm² (wavelength:365 nm), and allowed to cure at 120° C. for 1 hour, and then at 180° C.for 1 hour. The obtained cured films were evaluated conforming to themoisture permeable cup method (JIS Z0208), under environments of 40°C./90% and 25° C./50%, to calculate water vapor transmission rate.

TABLE 1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6Tensile fracture 74 83 70 77 75 79 strength (MPa) developability Yes YesYes Yes Yes Yes Aperture ratio (%) 89 82 92 89 88 86 Water vapor 8.513.2 7.9 8.3 8.1 8.7 transmission rate 25° C./50% (g/m² · 24 h) Watervapor 81.2 122.9 69.3 79.0 77. 1 80.5 transmission rate 40° C./90% (g/m²· 24 h) Comparative Comparative Example 7 Example 8 Example 9 Example 1Example 2 Tensile fracture 68 77 73 78 64 strength (MPa) developabilityYes Yes Yes Yes Yes Aperture ratio (%) 94 87 88 88 94 Water vapor 8.44.5 5.1 2. 1 2.4 transmission rate 25° C./50% (g/m² · 24 h) Water vapor78.3 33.9 37.1 16.2 24.8 transmission rate 40° C./90% (g/m² · 24 h)

As is clear from Table 1, Example 1 to 9 were large in the tensilestrength of the adhesive films, excellent in the film characteristics,and excellent also in the developability and resolution performance.

Next, Examples of bonded products obtained by bonding the semiconductorcomponent and the substrate using the above-described adhesive film willbe explained.

Example 1A to 9A and Comparative Example 1A to 2A

A 6-inch wafer having solid-state image sensors mounted thereon as thesemiconductor component was obtained, and each of the above-describedadhesive film was laminated on the 6-inch wafer using a laminator set to60° C. The film was then subjected to exposure through a negative maskusing an exposure apparatus, followed by development, to therebymanufacture a patterned sample. Shape and arrangement of the obtainedpattern were such as surrounding a light sensing portion of eachsolid-state image sensor, like a frame as wide as 100 μm. The exposurewas given so as to irradiate light of 365 nm to as much as 750 mJ/cm²,and the development was carried out using 3% TMAH (tetraammoniumhydroxide), at a pressure of spraying of 0.1 MPa for 90 seconds.Thus-obtained patterned sample were diced, and bonded to a glasssubstrate (5 mm×4 mm×0.5 mm) by thermocompression bonding(temperature=110° C., time=10 seconds, pressure=1 MPa). The obtainedsample was allowed to cure at 120° C. for 1 hour, and further at 180° C.for 2 hours, placed on a substrate for evaluation, and bonded, tothereby manufacture a sample to be evaluated. The sample to be evaluatedwas subjected to an accelerated reliability test generally adopted tosemiconductor devices. After being treated at 60° C., 90% humidity for500 hours, the sample was transferred to an environment of 25° C., 50%humidity, and whether dewing occurred or not inside the glass substrateof the sample to be evaluated was observed under a microscope. Resultsare shown in Table 2.

TABLE 2 Example 1A Example 2A Example 3A Example 4A Example 5A Example6A Evaluation of No dewing No dewing No dewing No dewing No dewing Nodewing dewing Comparative comparative Example 7A Example 8A Example 9AExample 1A Example 2A Evaluation of No dewing No dewing No dewing DewedDewed dewing

As is clear from Table 2, Examples 1A to 9A showed no dewing, nocorrosion on electrodes, excellent electro-conductivity, good image, anda desirable level of reliability. In contrast, Comparative Examples 1Ato 2A showed dewing, proving inferiority in the reliability ofsemiconductor devices. As judged from the results described in theabove, the present invention provides an adhesive film excellent inperformance, and excellent particularly in reliability as a material forcomposing semiconductor and liquid crystal devices.

1. An adhesive film used for bonding a semiconductor component or aliquid crystal display component with a substrate so as to obtain aspace formed therein, wherein said adhesive film is composed of a resincomposition containing a photo-curable resin, a thermosetting resin, anda filler, and said adhesive film shows a water vapor transmission rate,measured conforming to JIS Z0208 Method-B, of 30 [g/m²·24 h] or above,wherein said photo-curable resin contains an ultraviolet curable resinhaving an acrylic type compound as a major constituent.
 2. The adhesivefilm as claimed in claim 1, wherein said thermosetting resin contains anepoxy resin.
 3. The adhesive film as claimed in claim 1, wherein saidfiller contains a porous filler.
 4. The adhesive film as claimed inclaim 3, wherein said filler has an average void diameter of 0.1 to 5nm.
 5. The adhesive film as claimed in claim 3, wherein said fillershows an adsorptivity [Q1] under room temperature (increase in weight ofthe filler completely dried under heating and weighed in an aluminumcup, after being allowed to stay in a 25° C./50% environment for 168hours) of 7 [g/100 g filler] or above.
 6. The adhesive film as claimedin claim 5, wherein said filler shows an adsorptivity [Q2] at 60° C.(increase in weight of the filler completely dried under heating andweighed in an aluminum cup, after being allowed to stand in a 60° C./90%environment for 168 hours) of 3 [g/100g filler] or above.
 7. Theadhesive film as claimed in claim 6, satisfying 0.4×[Q1]<[Q2].
 8. Theadhesive film as claimed in claim 3, wherein said filler is zeolite. 9.The adhesive film as claimed in claim 1, wherein said adhesive filmshows a water vapor transmission rate, measured conforming to JIS Z0208Method-B, of 200 [g/m²·24 h] or below.
 10. The adhesive film as claimedin claim 1, wherein said adhesive film shows a water vapor transmissionrate at 25° C. (measured conforming to JIS Z0208, under conditions ofmoisture permeation treatment of 25° C./50%) of 4 [g/m²·24 h] or above.11. The adhesive film as claimed in claim 1, wherein said substrateshows a water vapor transmission rate, measured conforming to JIS Z0208Method-B, of less than 30 [g/m²·24 h].